CO/N 2, CO/Ar/O 2, and CO/N 2/O 2 gas mixtures are optically pumped using a continuous wave CO laser. Carbon monoxide molecules absorb the laser radiation and transfer energy to nitrogen and oxygen by vibration–vibration energy exchange. Infrared emission and spontaneous Raman spectroscopy are used for diagnostics of optically pumped gases. The experiments demonstrate that strong vibrational disequilibrium can be sustained in diatomic gas mixtures at pressures up to 1 atm, with only a few Watts laser power available. At these conditions, measured first level vibrational temperatures of diatomic species are in the range T V=1900–2300 K for N 2, T V=2600–3800 K for CO, and T V=2200–2800 K for O 2. The translational–rotational temperature of the gases does not exceed T=700 K. Line-of-sight averaged CO vibrational level populations up to v=40 are inferred from infrared emission spectra. Vibrational level populations of CO ( v=0–8), N 2 ( v=0–4), and O 2 ( v=0–8) near the axis of the focused CO laser beam are inferred from the Raman spectra of these species. The results demonstrate a possibility of sustaining stable nonequilibrium plasmas in atmospheric pressure air seeded with a few percent of carbon monoxide. The obtained experimental data are compared with modeling calculations that incorporate both major processes of molecular energy transfer and diffusion of vibrationally excited species across the spatially nonuniform excitation region, showing reasonably good agreement.